Hydrophilic and difficulty volatile biocidal triorganolead compounds

ABSTRACT

New triorganotin and triorganolead compounds which are hydrophilic and difficulty Volatile are used as biocides.

Bit? 399014 3313 HYDROPHILIC AND DIFFICULTY VOLATILE BIOCIDAL TRIORGANOLEAD COMPOUNDS [75] Inventors: Hermann Otto Wirth; Hans Joachim Lorenz, both of Bensheim-Auerbach; Hans-Helmut Friedrich, Philippstaal, all of Germany [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: July 25, 1973 {21 Appl. No.: 382,633

[30] Foreign Application Priority Data Aug. 4, 1972 Germany..... 2238360 July 6, 1973 Germany 2334383 [52] US. Cl 260/437 R; 71/97; 106/15 R;

106/15 AF; 106/297; 106/308 Q; 260/45.75 R; 260/270 R; 260/429 K; 260/999 [51] Int. Cl? C07F 7/24 [58] Field at Search 260/429.7, 437, 270 R [56] References Cited UNITED STATES PATENTS 2,641,596 6/1953 Leistner et 211.... 260/429.7

2,704,756 3/1955 Leistner et al.. 260/429.7

2,786,813 3/1957 McDermott 260/429.7

2,832,750 4/1958 Weinberg 260/429'.7 X

2,870,182 1/1959 Leistner 260/429.7

2,872,468 2/1959 Leistner et a1 260/429.7

2,912,448 11/1959 Ramsden 260/429.7

2,997,496 8/1961 Dorfelt et al. 260/429.7

[451 Aug. 26, 1975 3,015,644 1/1962 Leistner et a1 260/429.7 X

3,073,854 1/1963 Ballinger 260/437 R 3,081,325 3/1963 Ballinger 260/437 R 3,095,434 6/1963 Stamm et a1... 260/429.7 3,115,509 12/1963 Mack 260/429.7 3,129,236 4/1964 Weissenberger... 260/429.7 3,147,293 9/1964 Giraitis et al. 260/437 R 3,242,201 3/1966 Cramer et a1 260/429.7 X 3,322,779 5/1967 Henry et a]. 260/437 R X 3,395,164 7/1968 Leebrick 260/429.7

3,417,117 12/1968 Davies 260/429.7 3,538,088 11/1970 Hartmann... 260/429.7 X 3,649,662 3/1972 Wirth et 260/437 R 3,793,356 2/1974 Williams 260/429.7 3,798,249 3/1974 Overmars et a1 260/437 R X FOREIGN PATENTS OR APPLICATIONS 1,020,331 12/1957 Germany 1,020,331 8/1962 Germany 1,020,331 I/1963 Germany 1,020,331 10/1963 Germany 12/1967 Germany 8 OTHER PUBLICATIONS Shapiro et al., The Organic Compounds of Lead, John Wiley & Sons, N.Y. pp. 247-254 (1968).

Primary ExaminerI-Ie1en M. S. Sneed Attorney, Agent, or FirmLuther A. 'R. Hall; Nestor W. Shust 57 ABSTRACT New triorganotin and triorganolead compounds which are hydrophilic and difficulty Volatile are used as biocides.

23 Claims, No Drawings HYDROPHILIC AND DIFFICULTY VOLATILE BIOCIDAL TRIORGANOLEAD COMPOUNDS Triorgano-tin and triogano-lead compounds are valuable biocides. However, the widely used compounds, for example bis-(tri-n-butyl-tin)-oxide (TBTO) or triphenyl-lead acetate (TPLA), are highly hydrophobic in accordance with their chemical constitution. Their low water-solubility (that of TBTO is only ppm) severely limits their field of use. It is extremely difficult to manufacture aqueous disinfectant solutions with them or to add them to disperse paints. The frequently used admixture with emulsifiers, for example, in the form of the commercial product METATIN R 5710 (based on TBTO), is a long way from being able to satisfy all the requirements of practice because these emulsions have only limited durability A further disadvantage, particularly of the trialkyl tin compounds, is their volatility. This volatility is the cause, for example, of the rapid loss of effectiveness of TBTO and its derivatives in many practical applications.

All tributyl tin carboxylates, sulphonates,-and salts with inorganic acids (chloride, sulphate, nitrate, perchlorate etc.) undergo hydrolysis on contact with water and consequently reconversion into volatile TBTO. Even more marked is the volatility in compounds with smaller organic radicals, especially the trimethyl tin derivatives. However, these compounds are of considerable commercial interest because the biocidal activity spectrum in the triogano-tin series is highly specific as to structure.

This invention therefore has for its object to develop biocidal triorganometallic compounds with hydrophilic properties which are soluble in water, or at least are readily compatible with or form stable emulsions with water, and which still continue to possess only a slight volatility. The surprising discovery has been made that it is possible to effect the hydrophilic modification and reduction of the volatility with a single structural principle. The hydrophilic solubilising groups which impart the water-solubility (compatibility) and simultaneously .also lower the volatility, are bonded through the mercapto-sulphur to the trioganometallic radicals. Only this bond ensures a hydrolysis-resistant fixing of the solubilising groups mentioned.

- A number of triorganometallic mercaptides with biocidal activity have already been proposed. For example, tributyl-tin-Z-diethylaminoethyl mercaptide is claimed as fungicide in French Pat. No: 1,533,524.

Here too only the salt formation leads to a product with hydrophilic properties which are useful for practical purposes.

Tributyl-tin-B-hydroxyethylmercaptide is cited in US. Pat. No. 3,382,264. This compound contains a free hydroxy group. But this is still not sufficient for the hydrophilic solubilising of the tributyl tin group necessary for practical purposes. A satisfactory hydrophily is obtained only with two or more free hydroxyl groups, e.g., in the form of the monomercaptoglyceride.

Japanese Pat. No. 1977/67 claims organo-tin sulphaminates with a certain water-solubility. However, verification has shown that, for example, the tributyl tin sulphaminate is hydrolytically split off in water at once and passes over into TBTO. As further investigations have shown, only the mercapto compound (apart from the carbon bond) is able to prevent this hydrolysis.

The invention therefore provides hydrophilic, difficulty volatile biocidal compounds of the formula I wherein M represents tin or lead and R R and R each independently represents a linear or branched aliphatic group with 1 to 16 carbon atoms which can be saturated or singly olefinically unsaturated, the cyclopentyl, cyclohexyl, or phenyl group, the sum of the carbon atoms of the substituents R R and R being altogether at most 18, and A represents a strongly hydrophilic group with polyol, polyether, carboxylate, sulphonate, carboxylic acid ester, carboxylic acid amide, and/or ammonium salt function.

The application also provides a process for the manufacture of compounds of the general formula I, wherein a triorganometallic compound of the general formula II in which M, R R and R have the same meaning as in formula I and X represents OH, O chlorine, bromine, iodine, or acetate, is condensed in known manner with a mercapto compound of the general formula III HSA

(III) in which A has the same meaning as in formula I, optionally in the presence of a basic compound, accompanied by the elimination of HX.

As triorganometallic compounds of the formula Ill there are used especially triorganometallic hydroxides or triorganometallic oxides.

The symbol in formula I preferably represents tin and R,, R and R represents a linear or branched alkyl or alkenyl group with l to 4 carbon atoms, the cyclohexylor the phenyl group.

Preferably two or all three of the groups R R and R are the same. If two alkyl groups are the same, these are preferably methyl groups.

Exemplary of R R and R in the general formula 1 are n-amyl, 2-methylbutyl, 3-methylbutyl, neopentyl, pentenyl-B, pentenyl-4, 3-methyl-butenyl-3, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, cyclopentyl, but preferably methyl, ethyl, vinyl, n-propyl, i-propyl, n-butyl, i-butyl, butenyl-B, cyclohexyl, or phenyl.

Preferred triorganometallic groups are: tri-n-butyltin, triphenyl tin, tricyclohexyl tin, octyl-dimethyl tin, cyclohexyldimethyl tin, phenyl-dimethyl tin, and triphenyl lead.

A represents in detail:

1. The radical of a polyol with 2 to 6 hydroxyl groups which can also be substituted by an aldehyde group, or of a polyethylene oxide switch with 2 to 15, preferably 8 to l 1, ethylene oxide units.

2. A hydrocarbon radical with carboxylate or sulphonate function, of the formula IV and q /2 in the second. Y is preferably sodium or the ammonium group HN(CH -Cl-I. ,OH)

The group X can also be 3. A hydrocarbon radical with carboxylic acid amide or, in particular, carboxylic acid ester, function, of the formula wherein Q and p have the meanings given hereinbefore, Q is preferably hydrogen and p is preferably 1 or 2, X

is -CO- and q is 1. Y is preferably a polyethylene oxide radical of the formula o (CH CH -O 1,, H

in which n is 2 to 15, especially 8 to 1 l, apolyhydroxyalkyl radical of the formula -l-(CH).

in which Mr is 2 to 6, or the polyhydroxyalkyl radicals which dereive from pentaerythritol, dipentaerythritol, and trismethylolpropane CHE-CH -OCH. ,CCH OH Y is also the radical of primary or secondary aminepolyethylene oxide adducts of the formula wherein r and s are numbers which are the same or different. The sum of r-l-s is 2 to 15, preferably 2.

The values for m, n, r, and s in the radicals cited hereinbefore can also be rational numbers for mean values of the chain length of the given radicals.

4. A hydrocarbon radical with an ammonium salt function, of the formula wherein Q and p have the meanings given hereinbefore and p is preferably 2, X in its turn corresponds to the formula -NZ and Z represents lower alkyl groups which are the same or different, polyethylene oxide radicals with 2 to 6 ethylene oxide units, and/or hydrogen, but preferably ,B-hydroxyethyl.

The group X can also be CH-CO29,

and Y represents a monovalent or divalent negative counterion, wherein in the first case q 1 and in the second q /2.

In the formula I 'SA preferably represents the radical of a salt of an aliphatic mercaptocarboxylic acid with at most 8, but above all at most 5, carbon atoms, and, in particular, represents the 2-mercaptopropionate or mercapto-acetate radical, wherein sodium, potassium or the triethanolamine group is preferred as cation, and very preferably S-A is the radical of the triethanolamine salt of thioglycolic acid. in addition SA is preferably the radical of an ester of an aliphatic mercaptocarboxylic acid with up to 8, especially up to 5, carbon atoms, in particular of 2-mercaptopro- Examples of -X as NZ group are ad 4. NH NH (CH NH (C H NH (CH2CH2OH)2, NH (C H 2 2 N 2 5); N 3) 2'- 2- )2 H2 H2 13 (n is l to 6) Examples of the group Y are ad 2. A counterion which is positively charged once or twice ad 3. Polyhydroxyalkyl or polyethylene oxide radi- O cals or the radical of amine-polyethylene oxide adducts (n is 2 to 15, preferably 8 to ID) Examples of the group are ad. 2. Carboxylate or sulphonate radicals 'ad 3. Carboxylic acid ester or carboxylic acid amide radicals OH OH OH OH OH (n is 2 to 15, preferably 8 to 11) ad. 4. Monoor divalent negative counterion Cl, Br, I, F, NO BF CH -S0,, P' 3 6 4) a a SiF F CCO Cl C-CO The triorganotin or triorgano-lead polyolmercaptides are manufactured by reacting the free mercaptans with a triorgano-tin or triorgano-lead oxide or hydroxide,

for example Ph,,Pb-OH+ Hs cH,-cH cH Ph=Phenyl) OH H The synthesis can also be carried out starting from triorganometallic halide in the presence of alkali lye,

0 carbonate, or bicarbonate solution on the, lines of a SCHOTTEN-BAUMANN reaction, e.g.,

and mercaptopolyethylene oxides are obtained by the addition of polyethylene oxide to hydrogen sulphide The manufacture of the triorganoztin or triorganolead mercaptoalkylsulphonates of the formula can be carried out, for example, in thefollowing way (H2C)=. +NaSH Hs cH. so Na.

Using an ion exchanger (AT) it is possible to obtain therefrom the free sulphonic acid -SO Na AT H-*-* -SO H AT. Na

which can be converted with the bases Y. OH into other salts, with the equation The direct reaction with, for example, KHS, leads to the same result. Finally, the ,B-mercaptoethanesulphonic acid can also be obtained by startin from the carbylsulphate.

The mercaptohydroxyalkylsulphonic acids can be easily obtained via the corresponding epoxides, e.g.

The synthesis route to the analogous triorgano-tin or triorgano-lead mercaptocarboxylic acid salts also proceeds via the corresponding mercaptocarboxylic acids,

for which there are a number of known methods of manufacture.

The reaction (neutralisation of the carboxyl group) with the base Y is carried out advantageously after the iinkage with the triorganotin or triorgano-lead group in accordance with the equation I.

The corresponding mercapto-hydroxyalkylcarboxylic acids can also be obtained via the epoxycarboxylic acids by known methods.

Triorgano-tin or triorgano-lead derivatives which carry a hydrophilic carboxylic acid ester function are manufactured in two steps.

The reaction with a triorgano-tin or triorgano-lead oxide or hydroxide is performed after the esterification of the mercaptocarboxylic acid with a hydroxyl group of the polyol. The monoesterification with respect to a chemically unitary polyolmonoester is as a rule only possible with a substantial excess of polyol. The separation of excess (nonreacted) polyol is effected in these cases very smoothly at the end stage after the combination with the triorgano-tin or triorgano-lead group, on the basis of differing solubility properties, principally in chloroform or methylene chloride. However, the polyol esterification can also be carried out under stoichiometric conditions for the monoesterification. The products which are formed under these conditions do constitute statistical mixtures, but since the monoester derivative predominates are sufficiently hydrophilic.

If the polyol is obtainable as epoxide compound, the esterific'ation can be effected also by the indirect route, in which case unitary polyol monoesters are also formed. It is advantageous in this case to effect the linkage of the mercaptocarboxylic acid with the triorganotin or triorgano-lead group beforehand.

OH OH (Et is ethyl) In obtaining the triorgano-tin or triorgano-lead mercaptocarboxylic acid polyethylene oxide esters the esterification is carried out first, as with the polyol esters Since these polyethylene oxides also called polyglycols are mostly mixtures, the triorgano-tin or triorgano-lead compounds resulting therefrom are not =i HCIQ' =i 0 unitary products. Their commercial value is not HN thereby impaired. I

The triorganotin or triorgano-lead mercaptocarboxy- 5 C lic acid amides with hydrophilic amide component can v be readily manufactured from the corresponding trior- (ph phenyl) g 0r triorganO-lead mercaptocarboxylic acid Examples of compounds according to the invention esters, preferably from the methyl esters,.on the lines 10 are li d h i b l of an ester-amide exchange reaction, for example The following abbreviations are used: Me methyl,

H c=cii ,,sn-s CH -CH C HN(CH2CH2OH).

If amines which are polyethylene oxide adducts, and Pr propyl, Bu butyl, Am amyl, Hex hexyl, Oc therefore constitute mostly mixtures, are used, then =octyl, Ph=phenyl.

corresponding mixtures are also obtained as end prod- 2O uc t. This is not pre udical to the use of these products. Triogano-tin or triorgano-lead derivatives With ammonium salt function of the formula OH OH R (H;,CCHCH CH SnSCH CHCl-l OH OH H. RM 8 (C Y Me;,SnSCH -C ca ol-i),

R. HO

J n Pr sn s cH (CH) CH OH are easily manufactured. When n is 2, a B-mercaptoe- OH thylamme is used as starting product Ph PbSCH (CH) ,CHO HS CH CH NZ I OH which in its turn can be obtained by addition of the CH OH amine HNZ to ethylenedisulphide. It is possible to CH0 3 manufacture other mercapto amines in known manner by addition of hydrogen sulphide to amines with unsaturated ligands. 40 (H- -C=CH).-i C (CH).

The conversion into the ammonium salt takes place OH advantageously after the reaction with the triorgano-tin nBu;,Sn-S-CH -(CH)|iH or triorgano-lead compound. This is effected either with acid, preferably mineral acid, but more preferably by alkylating agents, for example dimethyl sulphate, 4 n Ph;,Sn-S-(CH CH --O),.H (n-7) p-toluenesulphonic acid esters, or alkyl nitrates, e.g. Ph;,Pb-S(CH -CH -O ),,H (nl0 nBu;,SnS(CH- ,CH O),,H (n-l4) l-Bu SnSCH CH,N(CH -CH OH) Me SO Ph;,PbSCH- ,CH-CO Na i-Bu:,SnSCH -CH N(CH CH -OH) so,Mc

l i OH Me I co Na nPr -,SnS-CH (i-Bu is isobutyl, Me is methyl) CH -co Na Finally, mercapto-hydroxyalkylammonium salts can be obtained from the readily accessible epoxides, for example from glycidyltrimethylammonium chloride.

H- i(CHCH N(CH,,);,.'Cl+H S co Na Ph;,Ph-SCH CHCO K matic ligands can be readily manufactured from the fl 2 -1 2 known mercaptoamines, some of which are obtainable commercially. The most important reaction step for one example of a pyridinium salt is H ..i\

-Continued ":1

OH OH OH OH co. Na cH. co.. Na

one and the same triorganometallic group derivatives which are miscible with water to a practically unlimited extent, while other display good emulsiying properties.

Table l Solubility properties of tributyl-tin derivatives General formula: (butyl);,Sn-SA A Solubility in water extremely good 8 0 CH good(tensidc-like behaviour CH CH-CH satisfactory OH OH Comparison bis( n-tributyl-tin )-oxide (TBTO) poor ppm) The solubilising effect of a particular hydrophilic group naturally depends also on the triorgano-tin or triorgano-lead species itself-Large organic radicals (e.g. amyl or phenyl) require for a specific water-solubility of the resulting compound stronger solubilising groups than small organic radicals (e.g., methyl).

The quaternary ammonium group produces a very strong (already extreme) solubilising effect. The triorgano-tin or triorgano-lead compounds provided therewith they are almost always honey -or wax-like substances are in most cases miscible with water in any proportion. Very marked is also the solubilising effect of the sulphonate group in the form of the alkali salts. These substances display the typical behaviour of tensides (soaps), i.e., they form mostly micellar solutions and thereby also lower the surface tension of the water. The influence of the counterion is here more marked than in the case of the ammonium salts. Coupled with the strongly hydrophilic quaternary ammonium ions for example with the tetra-(B-hydroxyethyhammonium group it is possible to obtain extremely good water-solubility.

With the corresponding carboxylates the watersolubility is reduced somewhat under otherwise comparable structural prerequisites. Substances with the typical behaviour of soaps are also available in the form of alkali salts. The aqueous solutions also display the alkaline reaction which is typical of alkali carboxylate soaps, and like these they form very stable emulsions.

Very similar are the solubility properties of the triogano-tin or triorgano-lead carboxylic acid esters and amides (with hydrophilic alcohol or amine moiety). It can be said that there is a direct connection between the hydrophily and consequently of the water-solubility on the one hand, and the number of the hydroxyl groups and the length of the polyethylene oxide radicals on the other. The same applies also to the pure polyol and polyethylene oxide derivatives. All these products have a honeyor wax-like consistency.

In the compounds according to the invention the triorgano-tin or triogano-lead bond is completely stable to hydrolysis in neutral medium. Only in a strongly acid or alkaline pH range does cleavage slowly commence.

The compounds of this invention are outstanding biocides. With them it is possible to manufacture aqueous disinfectant solutions which can be used with complete success in human and veterinary medicine. The disinfecting of seeds and wood conservation also from aqueous liquor are other fields of application for these substances. They can also be used with particular advantage as additives for pigment dye dispersions and disperse paints, both in respect of storage and of the long-lasting protective action of the coating. Furthermore these substances can be used in antifouling paints, whereby they prevent both the harmful growth of sea organisms and improve as a result of the hydrophilic radical the hydrodynamic properties on the shipss stem.

A further field of application for these substances is mucilage control in paper manufacture, thereby also simultaneously ensuring paper conservation.

Certain thermoplasts and elastomers, in particular PVC with plasticiser content, can be effectively protected by the substances again attack by microbes. An antistatic finish is thereby simultaneously provided.

The substances of the present invention are also valuable herbicides for various cultivated plants. In cotton growing they can be used as defoliants and desiccants.

=ln many cases the phytotoxicity of the triorganometallic compounds according to the invention is distinctly lower than of the corresponding known compounds, thereby ensuring their favourable use in plant protection. Their activity against phytopathogenic fungi in cereal disinfection extends, for example, over Fusarium nivale, Tilletia caries, Helminthosporium gramineum, Septoria nodorum. The activity against soil fungi comprises, for example, Fusarium oxysporum, Pythium debarynum, hizoctonia solani, Verticileum albo atrum.

In fungoid leaf infections the following species, for ex- 5 ample, are attached and destroyed: Botrytis cinerea, rust fungi, e.g., Cloromyces and puccinia, powdery mildews, e.g., Phytophthora and Plasmopara, Pseudoperonospera.

Compound 3 S|nSCH CH COO-(CH CH:-O),,.H (n-9) 4 (nC,H );,S1iSCH .COO.H.N(CH:CH OH 5 (n-C ,H,,hSn-S-(CH .COO,H.N(CH CH OH) 6 (n-C,H ,);,SnSCH .CO.N(CH CH OH) Table Microbiological Test Activity range in ppm Bacteria 1 2 3 I 4 5 6 Staphylococcus aureus SG 51 1 10 3 10 '30 10 30 SG 5 1 1 M6 10 10 30 30 3 Sarcina ureac SMB 81 10 3 10 3O 30 $1 Streptococcus faecalis NCTC 8619 g 1O 10 10 30 100 30 agalactiac M 100 3 3 3O 3O 3 Corynehacterium diphtc- FUR l0 3 3 3O 10 S1 roides Bacillus subtilis NCTC 6460 I0 3 3 3U 10 1 Mycohacterium phlei ClTM 61 3 3 3 i 3O 10 $1 Escherichia coli NCl'C 8195 10 30 x 10 30 300 3O RP 45410 l0 10 10 3O 300 30 Arizona paracolon 711.7,8 300 300 300 300 306 Salmonella pullorum VBlZ 300 300 100 300 300 30( gallinarum VBlB 300 300 cholerae-suis VBl B 300 300 100 300 300 300 Pasteurella multocida K753 l0 300 10 30 30 30 Pscudomonas fluorcscens 10 300 30 300 30 3O NClC 4755 Fungi Trichophyton gypseum CBS 30 30 1O 10 l0 l0 Fusarium spec. DAP 30 30 Pilz schwarzlich DAP 10 3Q Candida albieans CBS 30 31) 3 10 10 10 Hefe DAP 10 10 Hcfe rot DAP l0 l0 Aspergillus niger ATCC (1275 3O 30 10 I0 I l0 l0 flavus CBS 12062 30 30 3 l0 l0 l0 Penicillium funicu- CEB 329631 30 100 ll) 3O 1U 3U losum cxpansum SMC 36 3O 3() 3 l0 l0 l0 Trichoderma viride CEB 3334.2 100 l0 10 10 1(1 10 Fusarium oxysponum CBS 30 10 3 10 l0 l0 Chactomium globosum CBS 14851 10 10 3 10 $3 $3 Altcrnaria tenuis CBS 10426 30 10 3 10 $3 $3 Paccilomyces varioti CBS 30 l() 3 10 $3 $3 Stachybotrys atra CBS 32465 l0 l0 3 10 $3 $3 Pullularia pullulans CBS 10767 11) 3 l() 10 1(1 Coniphora cerebella CBS 10 30 10 10 10 Poria vaporia CBS 100 3 1() l() 10 Polystictus vcrsi- 100 30 100 30 30 EMPA 61 i color Lenzites abietina CBS 10 100 10 1U 10 .virulent strains Results of the test of growth resistance in the beer bottling plant of a brewery:

1. white pigmented disperse paint based on a finely dispersed polyvinylpropionate copolymer finished with (g of additive per kg of ready for brushing paint) tion is removed by circulation. Subsequently 60 parts of bis-( tri-n-butyl-tin)-oxide are added and the water of reaction is once more removed by circulation. The solvent is then distilled off under reduced pressure.

free from growth 3.25g 3.4 g 3.7 g 3.8 g 3.95g 4.25g 4.7 g 5.0 g 7,35g 2.65g 3.35g 3.35g 3.35g 3.7 g 3,95g 4.5 g 4.9 g 5.0 g 5.2 g

5.75 g 6.6 g (1.7 g 7.2 g

7 months 8 months 8 months 10 months l months l0 months months 10 months 10 months 1() months l2 months 12 months 13 months 13 months 13 months 13 months 13 months 13 months l3 months 13 months 13 months 13 months 13 months l3 months 13 months 13 months 13 months 2. White pigmented disperse paint based on a finely dispersed styrene-butadiene copolymer finished with (g of additive per kg or ready) for brushing paint) Yield: l5l parts (99% of theory); colourless liquid;

Sn calc. l5,5%, found l5,6%

free from growth 3.35g 3.35g 3.95g 4.5 g 4.9 g 5.0 g 5.2 g

5.75g 6.6 g 6.7 g

7.2 g 7.75g 3.7 g 7.95

7 months 7 months 9 months l0 months 10 months l0 months lo months l0 months 10 months 10 months I l months 1 months I months I months 1 months 1 months 1 months l months I months months I months months months months months months The tin and lead compounds are used in these experiments in the same molar ratio.

S-tri-n-butyl-tin-thioglycolic acid polyethylene glycol 80 parts of polyethylene glycol (MG-400), 18,4 parts of thioglycolic acid, and .100 parts of toluene are heated under reflux with stirring until the water of reac- EXAMPLE I:

ester Batch: 20 parts of polyethylene glycol (MG-2(')0) 9.2 parts of thioglycolic acid 30 parts of his-(trin-butyl-tin)-oxidc parts of toluene Yield: 54 parts (97,5% of theory); colourless liquid:

n 1.5012. SN calc. 21,4%, found 209%.

Example III:

S-tri-n-butyl-tin-B-mercaptopropionic acid polyethylene glycol ester (C 11 Sn.SCl-l Ch COO-(CH CH O-),,I-l

The synthesis is carried out under the conditions described in Example 1.

Batch: 80 parts of polyethylene glycol (MG-400) 21.2 parts of fl-mercaptopropionic acid 60 parts of bis-(tri-n-butyl-tin)-oxide 100 parts of toluene Yield: 154 parts (99% of theory); yellowish liquid;

n 1.4921 Sn calc. 15.3%, found 15.2%

Example IV:

S-tri-butyl-tin-,B-mercaptopropionic acid polyethylene glycol ester (C H The synthesis is carried out under the conditions described in Example I.

Batch: 20 parts of polyethylene glycol (MG-200) 10.6 parts of Bmercaptopropionic acid 30 parts of bis-(tri-n-butyl-tin)-oxide 100 parts of toluene The reaction product was filtered over a filter aid.

Yield: 51 parts (88% by theory); colourless liquid;

n 1.4990. Sn calc. 20.6%, found 20.2%.

EXAMPLE V S-tri-n-butyl-tin-mercaptosuccinic acid-bis-polyethylene glycol ester The synthesis is carried out under the conditions described in Example I.

Batch: 40 parts of polyethylene glycol (MG-200) parts of thiosuccinic acid 30 pans of biS-(trim-butyl-tin)-oxide 100 parts of toluene The reaction product was filtered over a filter aid.

Yield: 79 parts (98,5% of theory); colourless liquid;

n 1.5000. Sn calc. 14.8, found l4,7%.

Example VI S-triphenyl-tin-,B-mercaptopropionic acid-polyethylene glycol ester Ph Sn.S-Ch Cl-l -(CH CH O) nh (n-9) The synthesis is carried out under the conditions described in Example I.

Batch: 26.5 parts of fi-mercaptopropionic acid 100.0 parts of polyethylene glycol (MG-400) 99.0 parts of triphcnyl tin hydroxide 200.0 parts of toluene While stirring, 100 parts of polyethylene glycol (MG-400), 26.5 parts of ,B-mercaptopropionic acid, and 200 parts of toluente are heated under reflux until the water of reaction has been quantitatively removed by circulation. A solution of 27 parts of sodium carbonate in 50 parts of water and 140 parts of triphenyl lead acetate are subsequently added and the batch is stirred for 30 minutes at the same temperature, Undissolved material is then filtered off, the filtrate dried over sodium sulphate, and the solvent distilled off under reduced pressure.

Yield: 183 parts (80% of theory); yellow oil. Pb calc.

21.4%, found 21.0%.

30 EXAMPLE VIII:

l-( S-trimethyl tin )-mercapto-polyethylene oxide (CH SnSCh CH O ),;H (n 10) liquid. Sn calc. 19.6%, found 18.4%. S calc. 5,0%,

found 4.8%.

EXAMPLE IX 1-( S-trivinyl tin)-mercapto-polyethylene oxide (CI-l =CI-l) Sn.S(CH --CH CH2O)HH (n-8) The synthesis is carried out under the conditions described in Example VIII.

Batch: 36 parts of l-mercapto-polycthylene oxide (n-8) 22 parts of trivinyl tin hydroxide 100 parts of toluene Yield: 54 parts (96% of theory); yellowish viscous liquid; Sn calc. 21,2%, found 2l,2%. S calc. 5,7%,

found 5.55%

Example X 1-(S-tri-n-butyl tin)-mercapto-polyethylene oxide (C 11 Sn.S(CH Ch. ,O),,H (n-l4) The synthesis is carried out under the conditions described in Example VIII.

Batch: 62 parts of l-mercapto-polycthylene oxide (n- I4) 30 parts of bis-(tri-n-butyl tin)-oxide 100 parts of toluene Yield: 90 parts (98% of theory); yellowish viscous liquid. Sn calc. 13.1%, found 12.9%. S calc. 3,5%, found 3.4%

EXAMPLE XI: S-tri-n-butyl tin tin-mercaptodiethanol 4 9):s 2 2rn2- )2"- "While stirring, a mixture of 60 parts of bis-(tri-nbutyl tin)-oxide, 24.4 parts of 'mercaptodiethanol, and 100 parts of toluene is stirred under reflux until the water of reaction is quantitatively removed by circulation. The solvent is subsequently distilled off in vacuo.

Yield: 81 parts (99% of theory); colourless liquid;

n 1.5168. Sn calc. 28.9%, found 28.8%

EXAMPLE XII S-tri-butyl tin-thioglycerol (C H -,Sn--SCH CI-I (OH)-CH -OI-I The synthesis is carried out under the conditions described in Example XI.

Batch: 30 parts of bis-(tri-n-butyl tin)-oxide 10.8 parts of thioglycerol I 100 parts of toluene Yield: 39 parts (98,3% of theory); colourless liquid;

n,," 1.5178. Sn calc. 29,8%, found 30.1%

EXAMPLE XIII: l-(S-triphenyl lead)-mercaptosorbitol The synthesis is carried out under the conditions described in Example XI. I

, Batch: 20 parts of -mercapto-sorbitol 45.5 parts of triphenyl lead hydroxide 100 pans of tolene n Yield: 63 arts 99% of theory); white powder; m.p.

v 210C (with decomp.) Pb calc. 32,7%, found 1 32.4%. S calc. 5,0%, found 5.1%.

EXAMPLE XIV ,B-(S-tri-i-butyl tin )-mercaptopropionic acid-l 1,1-trismethylolpropane monoester While stirring, 1072 parts of l,l,l-tris-(hydroxyme- 65 thyl )-propane, 21.2 parts of B-mercaptopropionic acid, and 250 parts of toluene are heated under reflux until the water of reaction has been quantitatively removed by circulation. Subsequently 60 parts of bis-(tri-i-butyl tin)-oxide are added and the water of reaction is once more removed by recirculation. The solvent is then dis- 5 tilled off under reduced pressure, and subsequently excess tris-(hydroxymethyl)-propane is distilled off in an oil pump vacuum.

Yield: 101 parts (99% of theory); honey-like consistency. Sn calc. 23.2%, found 23.0%. S calc. 6,3%, found 6.0%.

EXAMPLE XV sodium S-tri-n-butyl tin-thioglycolate (C I-I SnSCI-I CO .Na

While stirring, 29.8 parts of bis-(tri-n-butyl tin)-oxide, 10.1 parts of thioglycolic acid, and 100 parts of toluene are heated under reflux until the water of reaction has been quantitatively removed by circulation. A solution of 4.4 parts of sodium hydroxide in 50 parts of methanol is subsequently added, the batch is heated under reflux for 10 minutes, and the solvent distilled off under reduced pressure.

Yield: 39.1 parts (97% of theory); Wax-like substance. Sn calc. 29.45%, found 29.2%.

EXAMPLE XVI calcium B-( S-tri-n-butyl tin)a-hydroxy-propionate [(C I-I ),-,SnSCH CH(OH )CO Ca The synthesis is carried out under the conditions described in Example XV.

Batch: 59,6 parts of bis-(tri-n-butyl tin )-oxide 26.4 parts of l-hydroxy-2-mercaptopropionic acid 200 parts of toluene 5.6 parts of calcium oxide Yield: 93 parts (98% of theory); whit powder; m.p.

The synthesis is carried out under the conditions described in Example XV.

Batch: 25.6 parts of bis-(tri-n-propyl tin )oxide 15.0 parts of thiosuccinic acid 100 parts of toluene 8.8 parts of sodium hydroxide 100 parts of methanol Yield: 44 parts of theory); soap-like consistency. Sn calc. 26.9%, found 26.4%. S calc. 7.3%,

found 7.2%

EXAMPLE XVIII potassium S-triphenyl tin-w-mercaptopropionate Ph,,Sn-S-CH -(-CH CH -COO. K

The synthesis is carried under the conditions described in Example XV.

367 parts of triphenyl tin hydroxide 16.2 parts of w-mcrcaptopropionic acid 100 parts of toluene 6.2 parts of potassium hydroxide 50 parts of methanol Batch:

Yield: 54 parts (98% of theory); wax-like consistency Sn calc. 21.6%, found 21.1% S calc. 5.8%, found 5.8%.

EXAMPLE XIX sodium S-tri-n-butyl tin-y-mercaptopropanesulphonate C 11 );,Sn-S CI-I CH CI-l -SO .Na

A solution of 60 g of bis-(tri-n-butyl tin )-oxide in 100 partsof toluene is added dropwise to a solution of 39 parts of sodium y-mercaptopropanesulphonate and 50 parts of water. While stirring under reflux the water is removed by circulation and the solvent is subsequently distilled off under reduced pressure.

Yield: 87 parts (93,1 of theory); colourless powder;

m.p. 260263C. Sn calc. 25.4%, found 25.0%. S calc. 13.7%, found 14.0%.

EXAMPLE XX Example XXI triethylammonium S-tri-n-butyl tin-thioglycolate (C H Sn'SCH -COOH.N(-CI-l CH OI-l) To a solution of 460parts of thioglycolic acid, 74.6 parts of triethanolamine and 100 parts of toluene are added 59.6 parts of bis-(tri-n-butyl tin)-oxide and the water of reaction is quantitatively removed by circulation while stirring. The solvent is subsequently distilled off in vacuo and the residue us recrystallised from acetonitrile.

Yield: 76,4 parts (72% of theory); colourless crystals;

m.p. 64-67C. Sn calc. 22.4%, found 22.3%

Example XXII triethanolammonium S-trin-buty1 tin-B-mercaptopropionate (C H Sn-S-CH CH COOH.N

2 2 The synthesis is carried out under the conditions described in Example XXI.

Batch: 53 parts of B-mercaptopropionic acid 74 parts of triethanolaminc 149 parts of bis-(tri-n-butyl tin)-oxide 150 parts of toluene Yield: 266 parts (98% of theory); yellow viscous liquid; n1); 1.5182. Sn calc, 21.8%, found 21.5%.

Example XXIII triethanolammonium S-triphenyl tin-thioglycolate Ph SnS.CI-l COOI-l. N( CH CH OH 3 36,7 parts of triphenyl tin hydroxide are added to a solution of 9.2 parts of thioglycolic acid, 14,9 parts of triethanolamine, and 100 parts of tetrahydrofuran and the batch is stirred for 1 hour under reflux. The reaction mixture is subsequently cooled to C and the precipitated product is filtered with suction and dried.

Yield: 41.4 parts (84% of theory); colourless crystals;

m.p. 1l6-118C Sn calc. 20.1%, found 20.2%. SH calc. 5.6% found 5.4%

Example XXIV triethanolammonium S-triphenyl lead-thioglycolate The synthesis is carried out under the conditions described in Example XXIII.

Batch: 43.9 parts (65% of theory); crystalline powder, m.p. 108-1 10C (with decomp.). Pb calc.

30,5%, found 30.4%. N calc. 2.1%, found 2.1%

Example XXV S-tri-n-butyl tin-thioglycolic acid diethanolamide While stirring 39.5 parts of tri-n-butyl tinthioglycolic acid methyl ester, 12.5 parts of diethanolamine, and 0.5 part of ammonium carbonate are heated in vacuo until no more methanol is distilled off.

Yield: 46,7 parts (96% of theory); colourless liquid;-

n 1.5252. Sl-l calc. 6.8%,

found 6.5%. Sn calc.

24.4%, found 24.1%

EXAMPLE xxvi' B-(S-triphenyl lead )-a-amino-propionic acid (S-triphenyl lead cystein) While stirring, 45.5 parts of triphenyl lead hydroxide, 12.1 parts of cystein, and 200 parts of methanol are heated under reflux for 30 minutes. The solvent is subsequently distilled off in vacuo and the reaction product is recrystallised from tetrahydrofuran/water.

Yield: 48 parts (86% of theory); crystalline powder; m.p. l40148C (with decom.) Pb calc. 37.1%, found 36.9% S calc. 5.7%, found 6.1% N calc. 2.5%, found 2.4%.

Example XXVII B-( S-tri-n-butyl tin )-mercaptoethyl-diethylmethylammoniummethylsulphate '3C.rHu)uSnSC uC uT( u :1)2 a Batch: 400 parts of polyethylene glycol (MG-400) CH 10.6 parts of B-mercaptopropionic acid 25.6 parts of bis-(tripropyl tin)-oxide 100 parts of toluene While stirring, 13.3 parts of diethylamino-ethane thiol, 5 100 parts of toluene, and 26.8 parts of bis-(tri-n-butyl tin)-oxide are heated under reflux until the water of re- Yleldl 71 Parts 0f 'y); Yellowlsh q action has been quantitatively removed by circulation. 11020? 14946 Sn Calcfound 160%- the solvent is subsequently distilled off in vacuo and the EXAMPLE XXXI residue treated with 100 parts of methanol and 12.6 parts of dimethyl sulphate. The batch is then heated 'P y fi' p p p under reflux for minutes while stirring, then cooled acldpolyethylene glycol ester and the solvent is distilled off under reduced pressure. s s

yield: 48 parts (97% of theory); soap-like consls- 15 y- Sn Calc- 217%, found The synthesis is carried out under the conditons described in Example 1. EXAMPLE XXVIII B-(S-triphenyl tin)'meFCaPtOethYI'diethylmethylammonium' 20 Batch: 80.0 parts of polyethylene glycol (MG-400) methylsulphate 21.2 parts of B-mercaptopropionic acid 68.0 parts of bis-(tii-n-pentyl tin)-oxide 100.0 parts of toluene 4 Yield: 159 parts (97% of theory): yellow liquid; n 1.4895 Sn calc. 14.5%, found 14.4%

The synthesis is carried out under the conditions de- EXAMPLE XXXII scribed in Example XXVII. potassium s tri methy1 tin--y-mercapto-propanesulphonate (CH SnSCH Cl-I CH SO .K Batch: 13.3 parts of diethylamino-ethane i i The synthesis is carried out under the conditions de- 33.0 parts of triphenyl tin hydroxide ib d i E l XIX 100 parts of toluene 100 parts of methanol 12.6 parts of dimethyl sulphate.

Batch: 19,4 parts of potassium 'y-mercaptosulphonate 50.0 parts of Water I h d d Yield: 50 parts 97% of theory) yellow resin. Sn Y 6 100. f l calc. 20.75%, found 20.5%. 401 0 EXAMPLE XXIX Yield: 34 parts(95% of theory); colourless powder; S-tri-vinyl tin-thioglycolic acid-polyethylene glycol Sn Cale 332% found 329% ester EXAMPLE XXXIII (CH =CH SnSCH -COO-(CH -CH -O) -H (N-4 5 magnesium S-tri-methyl tin-B-mercaptopropionate The synthesis is carried out under the conditions described in Example XV.

The synthesis is carried out under the conditions described in Example I.

Batch: 20.0 parts of polyethylene glycol (MG-200) 9,2 an f hi l li i Batch: 212 parts of fi-mcrcaptopropionic acid 21.7 parts of tri-vinyl tin hydroxide parts of tri-melhyl tin hydroxide 100 arts of t l 100:0 parts of toluene 8.1 parts of magnesium oxide 50.0 parts of methanol.

Yield: 46 parts (97.5% of theory); colourless liquid.

Sn calc. 25.1%, found 25.0%. I Yield 52 parts (98.5% oftheory); white powder; mp. 240C. Sn calc. 22.5%, found 22.0% Mg. calc. EXAMPLE XXX 4.6%, found 5.0%.

S-tri-n-propyl tin-B-mercaptopropionic EXAMPLE XXXIV acldpolyethylene glycol ester S-tri-cyclohexyl tin-B-mercaptopropionic 83 2;;; acidpolyethylene glycol ester The synthesis is carried out under the conditions deya 2 2 2 z )uscribed in Example I.

The synthesis is carried out under the conditions described in Example I.

Batch: 40.0 parts of polyethylene glycol (MG 400) 10.6 parts of B-mercaptopropionic acid 38.5 parts of tricyclohexyl tin hydroxide 100.0 parts of toluene Yield: 84 parts (98% of theory); yellowish liquid; Sn calc. 13.88%, found 136%. S calc. 3.75%, found 3.8%.

EXAMPLE XXXVI S-dimethyl-phenyl tin-thioglycerol CH OH OH A solution of 61 parts of dimethylphenyl tin bromide in 50 parts of methanol is treated with 10.8 parts of sodium methylate. The reaction mixture is stirred for 10 minutes at 30 C and subsequently 50 parts of ipropanol and 21.6 parts of thioglycerol in the form of a solution are added dropwise. The sodium bromide is completely precipitated by adding 100 parts of diethyl ether. The undissolved substance is filtered off and the filtrate concentrated in a rotary evaporator. The remaining solvent is stripped off with an oil pump.

Yield: 62 parts (93% of theory); yellowish liquid:

n,, :1.6OO9 Sn calc. 35.65%, found 35.9%.

EXAMPLE XXXVI S-dimethyl-n-octyl tin-thioglycerol CH OH OH The synthesis is carried out under the conditions described in Example XXXV.

Batch: 68.2 parts of dimethyl-noctyl tin-bromide 10.8 parts of sodium methylate 21.6 parts of thioglycerol 50.0 parts of i-propanol 50.0 parts of methanol Yield: 73 parts (99% of theory); yellowish liquid; n,, 1.5158 Sn calc. 32.16%, found 32.2%. S calc. 8.69%, found 8.5%.

EXAMPLE XXXVII S-dimethylphenyl tin-B-mercaptopropionie acidpolyethylene glycol ester To a solution of 30.6 parts of dimethylphenyl tin bromide and 50 parts of methanol are added 5.4 parts of sodium methylate and the batch is stirred for 10 minutes at 30C. The reaction mixture is subsequently 5 treated with 48.8 parts of B-mercaptopropionic acid polyethylene glycol ester and 50 parts of i-propanol.

The clear solution is concentrated in a rotary evaporator, and the residue is taken up with chloroform and purified neutral on silica gel (hydrated with 5% water). Subsequently the solvent is stripped off from the eluate. Yield: 63.5 parts (87% of theory); yellowish liquid; n,, :1.5326. Sn calc. 16.64%, found 16.9%. S calc. 4.50%, found 4.3%.

EXAMPLE XXXVIII S-dimethylcyclohexyl tin-B-mercaptopropionic acidpolyethylene glycol ester c sn s ci-i, cH. coo{cH,-cii, o} H The synthesis is carried out under the conditions described in Example XXXVIII.

3 Batch: 31.2 parts of dimethylcyclohexyl tin bromide 5.4 parts of sodium methylate 48.8 parts of B-mercaptopropionic acid polyethylene glycol ester 500 parts of methanol 50.0 parts of i-propanol The synthesis is carried out under the conditions described in Example XXXVII.

Batch: 34.2 parts of dimethyl-n-octyl tin-bromide 5.4 parts of sodium methylute 48.8 parts of ,B-mercaptopropionic acid polyethylene glycol ester 50.0 parts of methanol 50.0 parts of i-propanol Yield: 61.3 parts (90% of theory); yellowish liquid; n,, :1.4940. Sn calc. 15.85%, found 15.9%. S calc. 4.28%, found 4.1%.

EXAMPLE XL sodium S-dimethyl-n-octyl tin-y-mercaptopropanesulphonate A solution of 51.3 parts of dimethyl-n-octyl tin bromide in 150 parts of methanol is treated with 8.1 parts of sodium methylate. The reaction mixture is stirred for minutes at 30C and subsequently 26.7 parts of sodium -y-mercaptopropanesulphonate dissolved in 40 parts of water are added dropwise. The clear solution is treated with chloroform and purified neutral on silica gel. The eluate is concentrated in a rotary evaporator and the residual solvent is distilled off in an oil pump.

Yield 63 parts (96% of theory); semisolid mass; Sn

calc. 27.03%, found 26.2%.

EXAMPLE XLl S-dimethyl-n-butyl tin-,B-mercaptopropionic acid polyethylene glycol ester The synthesis is carried out under the conditions described in Example XXXVI].

Batch: 42.8 parts of dimethyl-n-butyl tin bromide 8.1 parts of sodiummethylate 43.2 pans of fi-mercaptopropionic acid polyethylene glycol ester 75.0 parts of methanol 75.0 pans of i-propanol Yield: 69 parts (93% of theory); colourless liquid; Sn calc. 24.08%, found 23.6% S calc. 6.50%, found 6.3%

EXAMPLE XLIl B-( S-dimethyl-n-dodecyl )-mercaptoethyldiethylmethlammoniummethylsulphate The synthesis is carried out under the conditions described in Example XXXVII.

" Batch: 13.3 parts of diethylamino-ethanc diol 33.5 parts of dimethyl-n-dodecylhydroxide 100.0 parts of toluene 12.6 pans of dimethyl sulphate 100.0 parts of methanol Yield: 57 parts (99% of theory); soap-like consistency. Sn calc. 20.59%, found 19.9%. S calc. 11.12%, found 11.3%.

We claim:

1. Triorganolead compounds of the general formula wherein R R and R each independently represents a linear or branched aliphatic group with l to 16 carbon atoms, which can be saturated or singly olefinically unsaturated, the cyclopentyl-, cyclohexyl-, or phenyl group, the sum of the carbon atoms of the substituents R,, R and R being at most 18, and A represents a strongly hydrophilic residue selected from the group consisting of a. polyethylene oxides with 2 to ethylene oxide units, b. carboxylates or sulphonates of the general formula wherein Q represents hydrogen or the hydroxyl group, p is a whole number from 1 to 6, X is CO SO the succinic acid radical, the p-phenyl sulphonic acid radical or the m-benzoic acid radical and Y represents an once or twice charged cation with q =1 in the first case and q /2 in the second case,

0. a carboxylic acid ester or a carboxylic acid amide of the formula IV, wherein Q and p have the same meaning given hereinbefore, X is CO, q is 1 and Y represents for the ester a polyethylene oxide radical of the formula O(CH -CH --O),,H, in which n is 2 to 15, a polyhydroxyalkyl radical of the formula in which m is 2 to 6, or radicals of glycerine pentaerythritol, dipentaerythritol or trismethylolpropane, and for 0 the amide the radical of primary or secondary aminepolyethylene adducts of the formulae wherein r is in the first case 1 to 15 and r and s in the second case are numbers which are the same or different, the sum of r and s being 2 to 15, and

d. an ammonium salt of the formula 1V, wherein Q and p have the meanings given hereinbefore and p is 2, X represents a radical of the formulae wherein n is 1 to 6, or NZ wherein Z represents lower alkyl groups, which are the same or different, polyethylene oxide radicals with 2 to 6 ethylene oxide units, B-hydroxyethyl and/or hydrogen and Y represents a monovalent or divalent negative counterion,

wherein in the first case q l and the second case (1 /2.

2. Compounds according to claim 1, of the formula I, wherein R,, R and R each independently represents an alkyl or alkenyl group with l to 4 carbon atoms, the cyclohexylor phenyl group.

3. Compounds according to claim 1, of the formula I, wherein the substituents R and R are the same.

4. Compounds according to claim 1, of the formula I, wherein the substituents R R and R are the same.

5. Compounds according to claim 1, of the formula I wherein R, and R represent methyl, and R represents butyl, octyl, cyclohexyl, or phenyl.

6. Compounds according to claim 1, of the formula I, wherein R R and R are the same and represent nbutyl, cyclohexyl, or phenyl.

7. Compounds according to claim 1, of the formula I, wherein SA represents the radical of a salt of an aliphatic mercaptocarboxylic acid with at most 5 carbon atoms, and which contain sodium, potassium, or the triethanolammonium group as cation.

8. Compounds according to claim 1, of the formula I, wherein SA represents the radical of an ester of an aliphatic mercaptocarboxylic acid S(CH ),,COO(CI-I CI-I O),,H wherep is l to 6 and n is 2 to 15.

9. Compounds according to claim 1, of the formula I, wherein SA represents the radical of the salt of a mercaptoalkanesulphonic acid with at most 6 carbon atoms.

10. A compound according to claim 1 of the formula wherein n has a value of about 15.

l l. A compound according to claim 1, of the formula 12. A compound 1, of the formula 13. A compound according to claim 1, of the formula 3 PI SCH2COOH.N(CHZCH. ,OH

14. A compound according to claim 1, of the formula wherein n has a value of about l0.

17. Compounds according to claim 1, of the formula I, wherein the polyethyleneoxide has 8 to 11 ethylene oxide units.

18. Compounds according to claim 1, of the formula I, wherein -S A represents the 2-mercaptopropionate or mercaptoacetate radical and which contain sodium, potassium or the triethanolammonium group as cation.

19. Compounds according to claim 1, of the formula I, wherein SA represents the 3-mercaptopropion sulphonate radical.

20. Compounds according to claim 1, of the formula I, wherein for the carboxylic acid ester or amide, Q represents in formula II hydrogen, and p is l or 2.

21. Compounds according to claim 1, of the formula I, wherein n in the O-(CH CH O),,-H radical is 8 to l l.

22. Compounds according to claim i, of the formula I, wherein the sum or r and s in the aminepolyethylene adduct is 2.

23. Compounds according to claim 1, of the formula I, wherein Z in the NZ -group of the ammonium salt is the ,Brhydroxyethyl radical. 

1. TRIORGANOLEAD COMPOUNDS OF THE GENRAL FORMULA 1
 2. Compounds according to claim 1, of the formula I, wherein R1, R2, and R3 each independently represents an alkyl or alkenyl group with 1 to 4 carbon atoms, the cyclohexyl- or phenyl group.
 3. Compounds according to claim 1, of the formula I, wherein the substituents R1 and R2 are the same.
 4. Compounds according to claim 1, of the formula I, wherein the substituents R1, R2, and R3 are the same.
 5. Compounds according to claim 1, of the formula I wherein R1 and R2 represent methyl, and R3 represents butyl, octyl, cyclohexyl, or phenyl.
 6. Compounds according to claim 1, of the formula I, wherein R1, R2, and R3 are the same and represent n-butyl, cyclohexyl, or phenyl.
 7. Compounds according to claim 1, of the formula I, wherein -S-A represents the radical of a salt of an aliphatic mercaptocarboxylic acid with at most 5 carbon atoms, and which contain sodium, potassium, or the triethanolammonium group as cation.
 8. Compounds according to claim 1, of the formula I, wherein -S-A represents the radical of an ester of an aliphatic mercaptocarboxylic acid -S-(CH2)pCOO(CH2CH2O)nH where p is 1 to 6 and n is 2 to
 15. 9. Compounds according to claim 1, of the formula I, wherein -S-A represents the radical of the salt of a mercaptoalkanesulphonic acid with at most 6 carbon atoms.
 10. A compound according to claim 1 of the formula
 11. A compound according to claim 1, of the formula
 12. A compound 1, of the formula
 13. A compound according to claim 1, of the formula
 14. A compound according to claim 1, of the formula
 15. A compound according to claim 1, of the formula
 16. A compound according to claim 1, of the formula
 17. Compounds according to claim 1, of the formula I, wherein the polyethyleneoxide has 8 to 11 ethylene oxide units.
 18. Compounds according to claim 1, of the formula I, wherein -S -A represents the 2-mercaptopropionate or mercaptoacetate radical and which contain sodium, potassium or the triethanolammonium group as cation.
 19. Compounds according to claim 1, of the formula I, wherein -S-A represents the 3-mercaptopropionsulphonate radical.
 20. Compounds according to claim 1, of the formula I, wherein for the carboxylic acid ester or amide, Q represents in formula II hydrogen, and p is 1 or
 2. 21. Compounds according to claim 1, of the formula I, wherein n in the -O-(CH2-CH2-O)n-H radical is 8 to
 11. 22. Compounds according to claim i, of the formula I, wherein the sum or r and s in the aminepolyethylene adduct is
 2. 23. Compounds according to claim 1, of the formula I, wherein Z in the NZ3 -group of the ammonium salt is the Beta -hydroxyethyl radical. 